Dialkyl-5-(oxanilamido) isophthalate couplers for color photography



United States Patent DIALKYL-S-(OXANILAMIDO) ISOPHTHALATE COUPLERS FORCOLOR PHOTOGRAPHY Stanley M. Parmerter, Wheaton, 111., assignor toEastman Kodak Company, Rochester, N. Y., a corporation of New Jersey NDrawing. Application March 16, 1953, Serial No. 342,719

9 Claims. (Cl. 95-6) This invention relates to color photography, andparticularly to color couplers for use in photographic emul- 810118.

The use in color photography ofcolor-forming compounds which react withthe oxidation or development product of primary aromatic aminodeveloping agents to form colored images upon photographic developmentis well known. The coupler compounds employed in this way may be addedto the developing solution or incorporated in the sensitive emulsion.

When used in the emulsion, the couplers must be soluble in the medium inwhich they are incorporated. In the case of direct incorporation ingelatin or other hydrophilic medium, as in Fischer U. S. Patent1,102,028, the couplers must have groups rendering them watersoluble,such as carboxylic acid groups. In the case of incorporation in anorganic solvent, as in Mannes and Godowsky U. S. Patent 2,304,940 orIelley and Vittum U. S. Patent 2,322,027, the couplers must-be solublein the organic solvent used to dissolve them.

In the manufacture of emulsions containing couplers, considerabledifliculty has been encountered in purifying couplers containingcarboxylic acid groups, prior to incorporating them in the emulsion.Because of the presence of the carboxylic acid radical, soluble saltsare formed which are diificult to purify by recrystallization. This isespecially true if there are two or more carboxylic acid groups in themolecule.

It is therefore an object of the present invention to provide a novelclass of color couplers which can be readily purified byrecrystallization. A further object is to provide color couplers whichcan be incorporated in gelatin emulsions either by direct incorporationor by dispersion when dissolved in organic solvents. Other objects willappear from the following description of my invention.

These objects are accomplished by using as the coupler a compound havingthe formula:

NHGOCONH R @mzoo 002 C5H11 I wherein R is attached either directly orindirectly in the meteor para position to radicalI and represents acoupling group such as a 5-pyrazolone or 'a phenol group. Z representseither an alkyl, e. g., methyl, ethyl, propyl, outyl, or an alkalimetal, e. g., sodium or potassium.

I have foundthatthe radical of isophthalic acid is a valuablesolubilizing' component for couplers which are incorporated directly ingelatin emulsions, but compounds containing this radical are difiicultto purify by recrystallization. If the esters of phthalic acid are usedinstead of the free acid, the compounds may be purified byrecrystallization, and the esters hydrolyzed to the free acid beforeincorporation in the gelatin emulsions. The compounds are thenintroduced into the emulsion as an alkali metal salt, usually the sodiumsalt.

The isophthalic acid esters of the couplers may also be incorporated inthe emulsion in solvent dispersion, as described in Mannes and GodowskyU. S. Patent 2,304,940 and Jelley and Vittum U. S. Patent 2,322,027.

The following compounds illustrate esters which may be used according tomy invention:

NHOOOONH- -OONH CHzOHz-C NHCO 02cm rHn amide 1-pheny1-3-{3- [2-(ZA-di-tert-amylphenoxy) -5- 3,5 dicarbometh- 'oxyoxanilamido benzamido1 benzamido}-5-pyrazol0ne NHCO- NHCO NHCOCONH O C OgCH; H I

0 CHzC O OH 1-pl1enyl-3-{3-[2- (2,4-di-tert-amy1phenoxy) -5-(3,5-dicarbomethoxyoxanilamido)benzamido] benzamido} 4 [4-(carb0xymethoxy -phenylazo] -5-pyrazo1one Compound 1 was prepared asfollows:

on l m 500cm Comzcmom-O-mrc 0-6 010 o CONE- 3 IIIHC o c ONH CI H 00cm-CONHCHzGHz-NHGO aHu In a ZOO-m1. Erlenmeyer flask equipped with astirrer glyoxyl-amido)isophthalate was added with good stirring. werePlaced -Q anhydrous Sodium 70 After two hours the solution with dilutedwith 100 m1. of fioeltgtebfl0glrlltroofifilgisfc fig13%;?2333/ water.The precipitate was filtered, washed v /ith water, Phenoxy)aminobenzamidon phenethyl} naph and dried. On crystalhzatlon fromacetomtnle 2 g. thamide. The mixture war warmed to 50 to dissolve (42%)0f White Powder melting at was the amine and 1.5 g. (0.005 mole) ofdimethyl S-(chloro- 75 tained.

Compound 2 was prepared as follows:

N'HCO C- H:

NBC 0 C ONH Dimethyl S-(chloroglyoxylamido)isophthalate O H: O O (I)Q-NHLHC] 01c o o 001 011300 O-rrnoooom CHaOO In a 100-ml. round bottomstandard taper flask equipped with a stirrer was placed 38 g. (0.3 mole)of oxalyl chloride. With good stirring at 8 g. (0.033 mole) of dimethylS-amino-isophthalate hydrochloride was added portionwise during tenminutes. After stirring for one hour the reaction mixture was left atroom temperature for five days. The excess oxalyl chloride was removedin vacuo and the residue was recrystallized from 375 m1. of dry benzeneto give 7.5 g. (75%) of white needles melting at 160-165 withdecomposition.

Compound 3 which is a colored coupler was prepared from compound 2 asfollows:

p-Aminophenoxyacetic acid was prepared by reduction ofp-nitrophenoxyacetic acid in aqueous solution over 5% palladium oncarbon, and the free amine obtained was converted to the hydrochloridefor storage. M. P. 222- 223 C. The desired coupler was then obtained bydissolving compound 2 in pyridine at 0 C. and treating the solution withthe diazotized aniline derivative at 0 0., followed by drowning thereaction mixture in cold, dilute hydrochloric acid, filtering andwashing with cold water on the filter.

The couplers of the invention are particularly adapted to use in one ofthe emulsion layers of a multilayer color film to form dye imagestherein by methods well known in the art. Compound 3 is representativeof colored COOOH:

CICOCONHQ QO5Hu 0 O CH;

COOCHa coupler compounds comprising a part of my invention which areuseful in emulsion layers for masking purposes as described in Hanson U.S. Patent 2,449,966.

The couplers may be incorporated into emulsion layers in the form oftheir alkali metal salts. This is accomplished by first heating thecoupler in alcoholic alkali to hydrolyze the isophthalyl ester groups,followed by dilution of the reaction mixture and-reducing the pH toabout 6.5 to 7.0. The solution of the alkali metal salt of the coupleris then incorporated in the desired amount into a melted silver halideemulsion and coated as usual.

When incorporating the couplers in solvent dispersion into an emulsionthe coupler may be heated in a suitable volume of a coupler solvent suchas dibutylphthalate at about 165 C. until solution is obtained and thissolution is milled into a gelatin solution containing a suitabledispersing agent. The resulting dispersion is then introduced into amelted silver halide emulsion.

Various photographic developing agents can be employed with the couplersof my invention. The primary aromatic amino developing agents aregenerally suitable including the phenylene-diamines and aminophenols.The alkyl phenylenediamines may be substituted in the amino group aswell as in the ring. Suitable compounds are diethyl-p-phenylenediamine,monomethyl-p-phenylene-diamine, dimethyl-p-phenylenediamine andp-aminophenol. These compounds are usually employed in the salt form,such as the hydrochloride or the sulfate which are more stable than thefree amines. All of these compounds have a primary amino group whichenables the oxidation product of the developer to couple with thecolor-forming compounds to form dye images.

The following developing solution is suitable for developinggelatino-silver halide layers containing colored couplers according tomy invention incorporated either directly in the emulsion or in solventdispersion:

Water to 1 liter.

It will be understood that the examples and modifications set forthherein are illustrative only and that my invention is to be taken aslimited only by the scope of the appended claims.

What I claim is:

1. A photographic silver halide emulsion containing a coupler compoundhaving the general formula wherein R is attached to a position ofradical I other than ortho and represents a group of atoms containing acoupling group capable of reaction with a primary aromatic amino silverhalide developing agent to form a dye, and Z represents a member of thegroup consisting of an alkyl group and an alkali metal.

2. A photographic silver halide emulsion containing C eHsa couplercompound having the general formula NBC 0 C ONE 5Hu(t.)

a Mt.)

wherein R is attached to a position of radical I other than ortho andrepresents a group of atoms containing a S-pyrazolone group capable ofreacting in the 4-position with a primary aromatic amino silver halidedeveloping agent to form a dye, and M represents an alkali metal.

3. A photographic silver halide emulsion containing a coupler compoundhaving the formula defined in claim 2 wherein R represents a group ofatoms containing a phenolic hydroxyl group the aromatic nucleus of whichcontains a position free to react with a primary aromatic amino silverhalide developing agent to form a dye.

4. A photographic silver halide emulsion containing a coupler compoundhaving the general formula COOM I I HGoGoNn-Q CONHCHzCEh-O-NHCO-Q 00MNHCOCONHQ ls u wherein M represents an alkali metal.

6. A photographic silver halide emulsion containing a coupler compoundhaving the formula 9 10 7. A photographic silver halide emulsioncontaining a 2 wherein R represents a group of atoms containing a 5-coupler compound having the formula pyrazolone group having an azo groupin the 4-position.

('JOaCHs 8. A photographic silver halide emulsion containing 9. Aphotographic silver halide emulsion containing a coupler compound havingthe formula defined in claim a coupler compound having the formula CO-H2 COaCHz 9) ClsHu ill OCHzC OOH Rcferences Cited in the file of thispatent UNITED STATES PATENTS 2,511,231 Weissberger et al. June 13, 1950

1. A PHOTOGRAPHIC SILVER HALIDE EMULSION CONTAINING A COUPLER COMPOUNDHAVING THE GENERAL FORMULA